Polyhydroxyl polyamino compounds



a 2,155,304 UflltCd States Patent Ofiice carted apparatus and involves a minimum of manipulative steps. As suitable w-ihalogen substituted C-a1kyl substituted POLYHYDROXYL'POLYAMINO COMPOUNDS rtriethanolamines there may be mentioned, for example,

5 'C-.(.2-chloromethyl )triethanolamine, C-(Z-chloroethyD- triethanolamine, C-(2-chloropropyl)-triethanolamine, O (2-.chlorobutyl)etriethanolarnine, C-(Z-bromomethy'D-tri Frederick C. 'Bersworth, East Orange, N. 1., and Albert E. Frost, Millis, Mass., assignors, by direct and mesne assignments, to The Dow Chemical Company, Mid- ,landMich acorporafionpof Delaware ethanolamine and IC-(Z-bromopropyl) -triethanolarnine.

As alkylene diamines useful in preparing the com- No Drawing. Application/February 20, 1953, 10 poundsoftliisinvention there may bement'ioned ethylene serial PTO-338,164 diamine, 'isopropy-lene diamine, trimethylene diamine, 8 Claims. (CL 260 584) N,N -dimethyl ethylene diamine, lN,N'-diethyl ethylene diamine, N,N'-diisopropyl ethylene diamine, N,N'-di-nprop yl ethylene diamine, N,N-dimethyl "trimethylene di- This invention relates to a new and useful class of amine, N,N-dibuty1 isopropyleue diamine, and 'N,N' dipolyhydroxyl polyamino compounds which are sequestern-propyl isopropylene diamine.

ing agents for heavy metal ions, including iron, in strongly In addition to the alkylene diamines and substituted 'acidto strongly alkalinesolution. 'a'lkylene diamiries mentioned above, 1,2-diaminocyclo- It is, therefore, .an object of this invention to prepare hexane and its N,N-dialkyl substituted derivatives may polyhydroxyl polyamino compounds which are capable 0 be used.

of sequestering heavy .metal ions, and particularly ferric A' preferred compound of this series is produced from iron, in stronglyacid to strongly alkaline solution. 1,2-diaminocyclohexane and C-(ZZ-chloromethyl)-trietha Another object is to provide intermediate compounds nolamineand is represented by the following formula:

'CHl-CH;

O 1 CH; HOCHr-GH: (EH-(1'! CHr-CHaOH N-crtroH-cnr-ri N-cm-cn-cnr' acorn-cm n l j H mil-onion useful for the textile industry and the soap industry .in The product is a sequestering .agentforeiron and-other the preparation of cleaning and detergent products. heavy metal ions sinstrongly alkaline solution.

Other objects and advantages 'of the invention will in The compounds of this invention possess usefuland inpart be obvious and in part "appear hereinafter. teresting proper-tiesas sequestering agents for heavy'imetal The'following invention comprises polyhydroxyl polyions.and, especiall-y .for iron, in strongly acid to :strongly amino compounds of the general formula: alkaline solution and even dissolve ferric hydroxide in HOCHr-CH: OH OH C'Hr-C'H OH N-orndin- 0H5) ,.N-Y-N- (0 H2) won-0 H -N Boom-ch, long-onion wherein Y is a bivalent alky'lene radical of two to three strongly alkaline solutions at room temperature. They, carbon atoms which may be unsubstituted or may bear therefore, have-broadapplication intthe textile .and leather one or more lower alkyl groups, such as those of one to industries, in cosmetic and soap preparations, in washing two carbon atoms; 11 is a positive integer, 1, 2, ,3 or 4; compounds, soaker alkali, glass and metal cleaning prep- R is 'a meniber of :the group consisting of hydrogen, arations, in electroplating, as antioxidants, additives to methyl, ethyl, n-propyl, isopropyl-and butyl radicals. lubricants and in numerous other applications for which The compounds of this invention may be :prepared .by sequestering agents may be employed. any of several methods. One of -these methods consistsin The compounds of this invention are generally pale reacting two molecular proportions of a suitable halogen yellow to orange viscid syrups having little or no odor. substituted C-alkyl substituted triethanolamine, such as, They are extremely soluble in-wateranditraqueoussdlu- C-(Z-chloromet'hyl)-triethanolamine, with one molecular tions of acids and bases, -a .property which presents conproportionof an alkyl'ene diamene 'bearing the desired su'bsiderable .difiiculty in the purification of these products. stituents 'R "and "Y under conditions so as to obtain a For the purpose of this inventiomihowever, ,it is not necmax imum yield of the desired product. essary to isolate the pure polyhydroxyl polyamino nem- A second method of preparation consists in reacting pounds since they areibest employed in aqueous solution. an appropriate w-amino-C-alkyl substituted triethanol- Their aqueous solutions are ratherstrongly'basic. amine derivative for example, C-(2-aminomethy1')-tri- The compounds of this invention possess interesting ethanolamine, with the proper'alkylene dihalide, such as, and useful properties as sequestering agents for heavy ethylene .dichloridedn-a two 'to one molar ratio. metal cations, especially in iron, in strongly acid 10 Although these compounds can 'be prepared by methstrongly alkaline solution.

ods other than those described above .and also by modifica- The insolubility of ferric hydroxide ;and some basic tions which will appear 'to those skilled in the art, we salts of the .ferric ion is well known. Aqueous solutions prefer 'to use the procedure followed in the specific exof ferrous compounds are rapidly oxidized 'to insolubl amples since 'it is easily carried out, requires no compliferric compounds in acid solutions and particularly Iin alkaline solutions. Triethanolamine and certain sugars can sequester iron in alkaline solution. However, they all suffer the disadvantage of being applicable only in alkaline medium; the sugars suffer the further disadvantage of decomposition in alkali, particularly on warming. The polyhydroxyl polyamino compounds of this invention are stable in alkaline and in acid solution, and possess a high solvent action on ferric hydroxide even in strongly alkaline medium.

The ability of our polyhydroxyl polyamino compounds to sequester ferric ion in alkaline solution depends upon their ability to form alcoholate type compounds which may be represented by the following general formula:

wherein the terms n, Y and R have the same significance as above.

In acid solution, the ferric ions are probably solubilized by the formation of compounds involving the nitrogen atoms of the diamine moiety.

This invention will further be illustrated by the following examples. It should be remembered that these examples are given primarily by way of illustration and the invention in its broader aspects is not to be restricted to these examples.

EXAMPLE 1 N ,N -di-( 2-hydr0xy-3-iminodiethanolpropyl) ethylene diamine (HOCH2CH2 zNCHzCHOHCHzNHCHzCHz NHCI-IzCHOHCHzN CHzCHzOH) 2 A solution of 0.4 mol (79.1'grams) of C-(2-chl0ro methyl)-triethanolamine in 250 milliliters of water was added dropwise over a 3-hour period to a Well stirred solution of 0.2 mol (12.0 grams) of ethylene diamine in 36 milliliters of water heated to slow reflux. A solution of 0.4 mol 16.0 grams) of sodium hydroxide in 100 milliliters of water was added as needed to keep the pH above 10. The solution was then refluxed for an additional 9 hours at the end of which time it was evaporated to dryness under reduced pressure and the viscous pale yellow residue extracted with absolute alcohol to remove sodium chloride. Evaporation of the alcoholic solution under reduced pressure gave a viscid yellow-orange liquid, soluble in water and alcohols and insoluble in other common organic solvents. This product is N,N-di-(2-hydroxy 3 iminodiethanolpropyl) ethylene diamine. Its aqueous solutions chelate iron and other heavy metal ions in strongly acid to strongly alkaline solutions and also dissolve ferric hydroxide in the cold at high pHs.

EXAMPLE 2 N ,N -di- 2-hydroxy-3-iminodiethanolpr0pyl -isopropylene diamine HOCI-IaCI-Iz zNCHzCHOHCHzNHCHa CH CH3 NHCHzCHOHCHzN CHzCHz OH 2 To 0.2 mol (14.8 grams) of isopropylene diamine in 25 milliliters of water heated to slow reflux there was added dropwise over a period of 2 hours, 0.4 mol (79.1 grams) of C-(2-chloromethyl)-triethanolamine in 250 milliliters of water. The pH of the solution was held above 10 by the gradual addition of 0.4 mol (16.0 grams) of sodium hydroxide. The reaction mixture was refluxed for 8 hours and then worked up according to the pro cedure of Example 1. The viscid yellow liquid, N,N'-di- (2 hydroxy- 3 -imindiethanolpropyl) isopropylene diamine, is soluble in water and alcohols (such as methyl, ethyl, propyl and isopropyl alcohols), and dissolves ferric hydroxide even at high pHs.

4 EXAMPLE 3 N,N-di-(5-hydr0xy-6-iminodiethanolhexyl)-N,N-

diethyl ethylene diamine I OH;

hydrogen chloride liberated during the reaction. After an additional 8 hours refluxing, the mixture was worked up as in Example 1. The product is a viscous yellow liquid soluble in water and alcohols and in aqueous solution. It sequesters heavy metal ions over a wide pH range.

EXAMPLE 4 N ,N di- (2-h ydroxy-3-iminodiethanol-propyl -N ,N

dimethylethylene diamine (HOCHzCHz 2NCH2CHOHCH2N(CH: CH:

CHzN CH3 CI-IaCHOHCI-IzN CHzCHzOH) 2 Four-tenths (0.4) mol (79.1 grams) of C-(3-chloromethyl)-triethanolamine in 250 milliliters of water was added dropwise over a period of 2 hours to 0.2 mol (17.6 grams) of N,N'-dimethyl ethylene diamine in milliliters of water heated to slow reflux. A solution of 0.4 mol (16.0 grams) of sodium hydroxide in 100 milliliters of water was added from time to time to remove the hydrogen chloride liberated. The solution was refluxed for 8 hours after which it was worked up as in Example 1. The viscous yellow liquid, N,N'-di-(2-hydroxy-3-iminodiethanol)-N,N'-dimethyl-ethylene diamine, is soluble in water and alcohols, and sequesters heavy metal ions, including iron, over a wide pH range.

EXAMPLE 5 N ,N '-di- (2-hydr0xy-3-iminodiethanolpropyl -trimeth ylene diamine (HOCHzCHz) zN-CHzCI-IOHCI-IaNHCI-IzCHa CH2NHCH2CHOHCH2N( CHzCI-IzOH) 2 Four-tenths (0.4) mol (79.1 grams) of C-(2-chloromethyD-triethanolamine in 250 milliliters of water was added over a 2-hour period to a gently refluxing solution of 0.2 mol (14.8 grams) of tn'methylene diarnine in 100 milliliters of water. A solution of 0.4 mol (16.0 grams) of sodium hydroxide in 100 milliliters of water was added from time to time to remove the hydrogen chloride liberated. After 8 hours of refluxing, the mixture was worked up as in Example 1. The viscous yellow product, N,N'- di (2-hydroxy-3-irninodiethanolpropyl)-trimethylene diamine, is very soluble in water and alcohols, and sequesters heavy metal ions over a wide pH range.

Compounds of the type described herein include two terminal triethanolamine residues in the chain of the molecule. The compound thus becomes capable of forming alcoholate type linkages which are effective to complex iron (ferric) in very strongly alkaline solution, e. g., in solutions of pH about 12 and greater.

Though the invention has been described with reference to only a relatively small number of examples, it is to be understood that variations thereof may be devised without departing from the spirit or scope of the invention.

What we claim is: 5. The compound N,N' di- (2-hydroxy-3-iminodieth 1. Chemical compound corresponding to the general anol propyl)-isopropylene diamine conforming to the formula:

wherein Y is a bivalent alkylene radical which places two formulai to three carbon atoms in the chain of the molecule be- 6. The compound N,N' di (5-hydroxy-6-iminodiethtween the nitrogen atoms; R is a member of the group ano1heXyl)-N,N'-diethyl ethylene diamine conforming to consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl the formula:

Boom-0H, 0H 01H; 01H; 311 CHr'CHgOH N-CHz-H(CH:)4--N-CHr-CH,N(CH1)4CHCH:N

HOCHr-C g CHr-CH OH and butyl radicals, and n is a positive integer from 1 7. The compound N,N'-di- (2-hydroxy-3-iminodieththrough 4. anol propyl)-N,N-dimethyl ethylene diamine conforming 2. A compound in accordance with claim 1, in which to the formula:

HOCHrCH: 0 (EH: $11 0 CHa-CHgOH N-OHr- HCH,NCHgCH;N-OH H-CH;-N

HOCHx-C 1 CH1-CH2OH R is hydrogen. 8. The compound N,N' di (2-hydroxy-3-iminodieth- 3. A compound in accordance with claim 1, in which anol-propyl)trimethylene diamine conforming to the forn is 1. mula:

Boom-0H, OH 1'1 1'1 OH CHr-CHzOH N-0H,- i:H-0H,N0H,-0H,-0H,N0H: JH0Hg-N Boom-G I CHFCHzOH 4. The compound N,N-di-(2-hydroxy-3-iminodiethanol propyl)-ethylene diamine conforming to the formula: 40

Boom-0H, o I H OH GIL-0111013 NCH: H-GHr-N-CHr-CHa- OHrH-GHr-N Room-c CHPCHOH No references cited. 

1. CHEMICAL COMPOUND CORRESPONDING TO THE GENERAL FORMULA: 